Ludwig paul



UNlTED STATES PATENT LUDVVIG PAUL, OF FilRST'EXBERG-ON-ODER, PRUSSIA,GERMANY.

PRODUCTION OF DISULPHO AND DICARBO ACIDS OF THE DIAMlDOAZO-BENZlDlNl-IS.

SPECIFICATION forming part of Letters Patent No. 380,402, dated April 3,1888.

Application filed August 16. 1857. Serial No. 247,113. (No speclmens.lPatented in France January 11,1887, No. 184,160; in Germany March 4,1887, No. 3,209 and July 12, 1887, No. 3,339, and in England June 9,1887, No. 8,296, and June ll. 1867,

To all whom it may concern.-

Be it known that I, Dr. LUDWIG PAUL, a citizen of the Empire of Germany,residing at Fiirstenberg-on-Oder, in the Kingdom of Prussia, in theGerman Empire, haveinvented certain new and useful Improvements in thePro duction of Disulpho and Dicarbo Acids of the Diamidoazo-Bcnzidines,of which the following is a specification.

This invention consists in the process or processes of producing monoand diamidoazo-benzidines, transformation of them into tetrazocompounds,and their combination with amines and phen ols, or thesulpho-acids ofthese bodies, and production of colors therefrom.

The tetrazo compounds known up to the present may be combined withaniline, toluidine, Xylidinc, and cumidine, as well as with thesulpho-acids of these bodies. I know as tetrazo compounds of thisspecies: (a) tetrazodiphenyl, tetrazo-ditolyl, tctrazo-diallyl; (b)tetrazo-diphenyl-dicarbon acid and its ethers; (c) tetrazo compounds ofthe ethers of diamido-diphenyl; (d) tetrazo-fiuorene andtetrazostilbene.

A. Dicmidoaeo bcneidines and colors derived from them.

Examplel: Tenpounds mctadiamidodiphen acid are diazotized, as usual, andmixed with the solution of 13.2 pounds chlorhydrate of alpha or betanaphthylamiue in thirty pounds water. After a rest of twelve hours theprecipitateis filtered, washed, stirred up in fifty gallons water, andboiled under addition of ammonia, with the alkaline reaction. Theammonia salt thus formed is precipitated by common salt and filtered. Ifthe 13.2 pounds chlorhydrate of naphthylamine are substituted by 6.6pounds chlorhydrate of alpha-naphthylamine a precipitate is formed witha free diazo group, which may be combined with a second molecule of anamine or phenol. By entering it into an aqueous solution of (a) sixpounds chlorhydrate of alpha or beta naphthylamine, or (b) 4.8 poundschlorhydrate of aniline, or (a) 5.3 pounds chlorhydrate of toluidine, or(d) 6.9 pounds chlorhydrate ofxyli dine, or (c) 7.4 pounds chlorhydrateof cumi dine, or the equivalent quantities of the sulphoacids of thesebodies, mixed colors are formed which dye the cotton yellowish inalkaline bath.

Example 2: The yellow coloring-matters ob tained by example 1, asammonia salts, are stirred up, still moist, in twenty-five gallons waterand four pounds hydrochloric acid and cooled. A solution of 5.2 poundsnitrite of soda is cautiously added, and during a rest of twelve hours astrong nitrous reaction results. The thus resulting tctrazo compound maybe filtered, which is preferable for further combinations with amines,or directly poured into a solution, which must be kept alkaline duringthe whole process, of twentysix pounds R. salt of beta-naphtholdisulphoacid, or 18.3 pounds of alpha or beta naphthol monosulphonate ofsoda. Blue precipitates are produced, dyeing cotton violet.

Example 3: The tetrazo compound formed by ten pounds metadiamidodiphenacid is slowly poured into an aqueous solution of 2 to 4.8 poundschlorhydrate of aniline, or 2 to 5.3 pounds chlorhydrate of toluidine,or 2 to 6.9 pounds chlorhydrate of xylidine, or 2 to 7.4 poundschlorhydrate of cumidine, and ammonia cautiously added to the alkalinereaction. If the tetrazo compound had been filtered, it is stirred upwith some water. The solution of the chlorhydrate of the amine is addedwith a quantity (equivalent to three to four molecules hydrochloricacid) of acetate of soda. In both cases yellow precipitates are formed,which are filtered and washed. All these colors are weakcoloring-matters for cotton.

Example 4: The moist precipitate resulting from example 3 by thecombination of one molecule tetrazo-diphenyl-dicarbon acid and, forinstance, two molecules aniline is stirred up in twenty-five gallonswater, eighteen pounds hydrochloric acid added, and boiled. Afterfiltering and cooling, the solution is diazotized by 5.2 pounds nitriteof soda. After some rest the solution, which has turned into abrownish-yellow, is poured into an aqueous solution of (0918.2 poundsnaphth ionate of soda and the same weight of acetate of soda; after arest of twenty-four hours it is filtered and poured into ammonia. Thecoloring-matter formed dyes the cotton red from alkaline bath.

This coloring-matter may be still once diazotized wholly or half. Bywholly diazotizing, for instance, scarlet coloring-matters for wool areobtained. Or (0) 26.2 pounds R. salt of betanaphthol disulpho-acid. Thismixture is to be kept alkaline. A red coloring-matter results. Or (a)18.3 pounds soda salt of the alpha or beta naphthol monosulphoacid. Redorange dyeing-colors are produced.

Example 5: Ten pounds benzidine are diazotized in twenty-five gallonswater, 26.5 pounds hydrochloric acid, (thirty per cent.,) and 7.6 poundsnitrite of soda. The solution of tetrazodiphenyl thus formed is pouredonto an aqueous solution of 2 to 9.8 pounds chlorhydrate of alpha orbeta naphthylamine, or 2 to 7.1 pounds chlorhydrate of aniline, or 2 to7.9- pounds chlorhydrate of toluidine, or 2 to 10.2 pounds chlorhydrateof xylidine, or two to eleven pounds chlorhydrate of cumidine, or theequivalent quantities of the sulpho-acids of these bodies, underaddition of a quantity of acetate of soda equivalent to three to fourmolecules of hydrochloric acid. The resulting bodies, as far as they arenot obtained from the sulpho-acids of aniline, toluidine, xylidine, andcumidine, are difficult of solution in water and spirit, but may beeasily diazotized.

Example 6: The diamidoazo compound resulting from ten pounds benzidineand 14.2 pounds aniline saltis, still moist, stirred up intwenty-fivegallons water and thirty poundshydrochloric acid. After cooling, 7.6pounds nitrite of soda in aqueous solution are cautiously added and themixture left for rest twelve hours. The thus-obtained new tetrazocompound is poured into an aqueous solution of one of the followingbodies: (a) 26.6 pounds naphthionate ofsoda, or (b) 37.8 pounds R. saltof beta-naphthol disulphoacid, or (c) 26.7 pounds soda salt of alpha orbeta naphthol monosulpho-acid. blue, and from c a violet,coloring-matter for cotton in alkaline bath is produced.)

Example 7: Ten pounds diamidoazo-benzidine,

solution arises, from which the coloring-matter, which dyes a morebluish-red shade than that derived from resorcin, is precipitated bycommon salt and filtered.

Example 9: If the tetrazo-diphenyl is substituted by the equivalentquantities of (a) tetrazro-diphenyl-dicarbon acid and its ethers,

(From a a red, from b a.

of the same or of different amines or phenols,

or with one molecule of an amine or phenol.

Example 10: Ten pounds benzidine are diazotized in the usual way, mixedwith an aque ous solution of 7.2pounds acetate of soda, and a solutionof 7.1 pounds aniline salt and six poundsacetate of soda in 6.5 gallonswater added. A red precipitate is at once formed and filtered after arest of one hour. This precipitate is stirred up in fifteen gallonswater with twenty-four pounds hydrochloric acid and diazotized with 3.7pounds nitrite of soda. After a rest of some hours the thus-obtainedtetrazo compound is poured into an aqueous solution of one of thefollowing bodies: (a) 37.5 pounds R. salt of beta-naphthol disulphoacid,or (b) 26.3 pounds soda salt of alpha or beta naphthol monosulpho-acid,(in both cases the mixture is to be kept alkaline,) or (a) 26.3 poundsnaphthionate of soda and thirty-six pounds acetate of soda. Thecoloring-matters resulting from these three cases are separated bycommon salt, filtered, and, if necessary redissolved. They dye cotton inalkaline batha., blue; b, violet; 0, red.

Example 11: In substituting the 7.1 pounds aniline salt in example 10 by7.9 pounds chlorhydrate of toluidine, or 10.2 pounds chlorhydrate ofxylidine, or 11 pounds chlorhydrateofcumidine,combinations result whichmay be combined in quite the same way with the same quantities ofnaphthol disulpho-acids and naphthol monosulpho-acids and naphthionatesas is set forth in example 10, and analogous colors are produced. Thecoloringmatters obtained in examples 10 and 11 derived from thenaphthylamine sulpho-aeids may be transformed into coloringmatterscontaining the alpha or beta naphthol sulpho-acids by diazotizing andboiling.

Example 12: In substituting the ten pounds diamidoazo-benzidine ofexamples 7 and8 by the equivalent quantities of one of themonoamidoazo-benzidines of examples 10 and 11,

similar bodies are produced, dyeing cotton with a more bluish shade.

Example 13: In substituting the ten pounds benzidines of example 10 bythe equivalent quantities of (l) metadiamidodiphen acid or itsethers,(2) tolidine or dixylyldianiine, (3) the ethers of diamido-diphenol, (4)diamidofluorene or diamido-stilbene, or their sulphoacids, similarbodies as the monoamidoazo-benzidine are produced, which may be alsodiazotized and combined with the equivalent quantities of 1%. salt ofbeta-naphthol disulphoacid, soda salt of alpha or beta naphtholmonosulpho-acid, alpha or beta naphthylamine sul pho-acids, or resorcin,and furnish blue, violet, and red coloring-matters which dye cotton inalkaline bath. The monoamidoazo-benzidine described in the precedingexamples may be combined with a second molecule of aniline or itshomologue, or their sulpho-acids, and furnish thus the same combinationswhich result ,from combining one molecule of the tetrazo compounds knowndirect with two molecules of the respective amines, as is mentioned inexamples 1 to 9.

Example 14: The monoamidoazo'benzidine resulting from example 10 isstirred up in water with six pounds acetate of soda and mixed with anaqueous solution of 7.1 pounds aniline salt. After twelve hoursrestsooner by agitatin g and heating-the redprecipitate is transformedinto a yellow one of the composition Diamidoazo-benzidine.

In the same way the combinations resulting from example 13 may becombined with another molecule of aniline, toluidine, xylidine,cumidine, or their sulpho-acids.

0. Transformation of the monoamidoazobenzi- (Zines into hydrorcylcombinations by boilingwith water, diaeotizing the thus-obtainedhydromyl combinations, and their combination with pine 0101s 02' amines.

In combining the known tetrazo compounds mentioned with one moleculealpha or beta naphthol,alphaor betanaphthylamine,aniline, toluidine,xylidine, cumidine, resorcin, or the sulpho-acids of all these bodies,combina tions are produced which contain still a free diazo group. Thisdiazo group may be completely transformed into the hydroxyl group byboiling with acidulated water, and in this manner the compounds notsoluble in alkali and showing few symptoms of a color nature before aretransformed into such soluble in alkali and dyeing the wool.

Example 15: Ten pounds benzidine are diazotized as usual and combined:(a) Under addition of 7 .2 pounds acetate of soda, with, first, 1.1pound chlorhydrate of aniline,- or, second, 7 .9 pounds chlorhydrate oftoluidine; or,third, 10.2 pounds chlorhydrate of xylidine; or, fourth,eleven pounds chlorhydrate of cumidine; or, fifth, 9.8 pounds alpha orbeta naphthylamine; or, sixth, 13.3pounds alpha or beta napht-hionate ofsoda; or, seventh, 9.3 pounds metasulphanil acid. After some restthe mixtures are heated to boiling and the boilingcontinned until a visibledelivery of azote has ceased. Those coloring matters resulting which arenot soluble in water may be made soluble by sulphonation. Thecoloring-matters obtained dye cotton yellow to red in alkaline bath.(0.) Under addition of 34.5 pounds ammonia, with, eighth, 7.8 poundsalpha or beta naphthol; ninth, 18.8 pounds soda salts of betanaphtholdisulpho-acids; tenth, 13.2 pounds soda salts of alpha or beta naphtholmonosulpho-acids, voluminous dark-colored precipitates are formed, whichare completely decomposed by boiling. The colors resulting fromnaphthols are made soluble in water by sulphonation.

Example 16: Coloring matters containing the naphthol sulpho-acids alsoresult by diazotizing the precipitates from the naphthylaminesulpho-acids and decomposing themby boiling with water. Boiling is,however, not necessary. The precipitate, for instance, fromnaphthionates in example 15 is mixed with twenty four poundshydrochloric acid, 3.7 pounds nitrite of soda, and left for rest twelvehours, then boiled, and the product treated as is said above in example15; also, the other amines combined with the known or the new tetrazocompounds may be further diazotized and combined anew with phenols oramines.

Having thus described myinvention, I claim as new and desire to secureby Letters Patent- 1. The combination of the following tetrazo compoundsknown at present: (a) tetrazo-diphenyl, tetrazoditolyl, tetrazo-dixylyl;(b) tetrazo-diphenyhdicarbon acid and its ethers; (c) tetrazo compoundsof the ethers of diamido-diphenol; (d) tetrazo-fluorene,tetrazo-stilbene, or the sulpho-acids of these bodies, with twomolecules aniline, toluidine, xylidine, and cumidine, or theirsulpho-acids, and the coloringmatters thereby produced, as set forth.

2. The transformation of the bodies resulting from the combination ofthe tetrazo compounds known up to the present with two equal ordifferent molecules of alpha or beta naphthylamine or theirsulpho-acids, aniline, toluidine, cumidine, xylidine, or theirsulpho-acids, into new tetrazo compounds, and the coloringmattersthereby produced, as set forth.

3. The decomposition of those compounds resulting by operation ofprocesses stated in claim No. 2, which contain amines or theirsulpho-acids, into compounds containing the corresponding phenols ornaphthols, or their sulpho-acids, by boiling water, and thecoloring-matters thereby produced, as set forth.

4. The combination of the new tetrazo compound resulting from operationof processes stated in claim No. 2, with (a) alpha or beta naphthol, (b)alpha or beta naphthylamine, or their sulpho-acids, and thecoloring-matters thereby produced, as set forth.

5.v The combination of one molecule of any of the known tetrazocompounds mentionedin claim No. 1 with only one molecule of aniline,toluidine, xylidine, or cumidine, or their sulphoacids, and thecoloringmatters thereby produced, as set forth.

6. The transformation of the monoamidoazo compounds resulting from theoperation of the processes stated in claim No. 5 into (iiazo compounds,and their combination with alpha or beta naphthol or their sulpho acids,or alpha or beta naphthylamine or their sulphoacids,

IIO

and the coloring-matters thereby produced, as t(40,) instead of the freediazo group, by boilset forth.

7. The diazotization of the diamidoazo compounds resulting from theoperation of the processes stated in claim No. l and of the monoamidoazocompounds resulting from the operation of the processes stated in claimNo. 5, and combination with resorcin or its sulpho-acids, and thecoloring-matters thereby produced, as set forth.

8. The transformation of the intermediate products resulting from thecombination of one molecule of the known tetrazo compounds mentioned inclaim No. l with one molecule of aniline, toluidine, xylidine, cumidine,alpha or beta naphthylamine, alpha or beta naphthol, resorcin, or thesulpho-acids of all these bodies, into bodies which contain the hydroXylgroup,

ing with water, and the coloring matters thereby produced, as set forth.

9. The transformation of the compounds resulting from the operation ofthe processes stated in claim No. 8, which contain naphthylaminesulpho-acids, into colors containing the alpha or beta naphtholsulpho-acids, by dia zotizing and boiling with Water, and thecoloring-matters thereby produced, as set forth.

In testimony whereof I have signed my name to this specification in thepresence of two sub: scribing witnesses.

LUDWIG PAUL.

\Vitnesses:

CARL BORNGRAEBER, ALFRED A. WHITMAN.

